Process for making sulphonated products



Patented Apr. 18, 1933 'PATENT- OFFICE.

UNITED STATES HANS KANTOROW'IGZ, or ennnm-wrmnnsnonnann ARNOLD 363mm, orsemen NEAR BERLIN, GERMANY, ASSIGNORS TO FETT'SAURE- UND GLYCERIN-FABRIKG. M. B. H1, 015 MANyHEIM, GERMANY PROCESS FOR MAKING SULPHONATEDPRODUCTS- No Drawing. Application filed April 9, 1932, Serial No.604,350, and in Germany .April 14, 1931.

possessed byturkey red oil and highly sulphonated neutral oils. Sincethe produc-' tion from fat bodies of sulphonated products which are freefrom, or poor in, neutral fat is a matter of technical importance,attempts have consequently been made to obtain such products by eitherstarting from ricinoleio acid and therefore from a hydroxy-acid, or,when using ordinary fatty acids or oleins, sulphonating these insolution, e. g. dissolved in acetic anhydride or in neutral oils, whichtechnically is a somewhat involved process; or, alternatively, to use avery large excess of sulphuric acid as solvent at low temperatures lyingbelow 15 C., which low cooling renders prosecution of the technicalprocess more difiicult. and to remove these quantities of acid, whichare very large from a technical point of view, by interposing adiaphragm purification in the course of the process. All thesecomplications and difficulties which arise in the sulphonation werecaused by the fact that the usual semi-drying or non-drying normalcommercial fatty acids begin to solidify at temperatures below +15 (1.,which technically is detrimental.

It has now been found that commercial oleic acids and oleins can besuccessfully sulphonated without the said aids if thesaidcommercial'oleic acids and oleins are previously, for instance bycooling down to 5 C.

" to +10 C., freed to a very large extent from solid constituents, thesaid commercial oleic acids and oleins rendered thinly liquid in thisway-being sulphonated at sufficiently' low temperatures by means ofsulphuric acid 'or other known sulphonating agents, and

then'freed from sulphonating agents which have not reacted bywashingoperations. In

this'way sulphonated commercial oleic acids and oleins are obtainedwhich dissolve to acid.

form clear solutions, are brightly coloured, have only a mild odour, andwhich as such, or in the form of their salts or derivatives, aresatisfactorily soluble in soft, neutral, hard or acid, cold or hotwater, always with notable formation of a stable froth, as well as withhigh stability-towards lime and boilmg, to form cleansing, emulsifying,dispersion, moistening, levelling and carbonizingagents and whichalsocan be used as a saponin substitute for froth fire extinguishingagents, for disinfecting purposes, combat ing insects, and also forbucking, fulling, sizing and dressing and also in the manufacture ofartificial silk, in which case they may also act at the same time asgreasing agents.

The sulphonated olein with cold test, which is made at low temperature,e. g. above 0 0., with cooled sulphonating agents, contains variablequantities of sulphonic acids which are not capable of being split upwith mineral acid in the usual way; thus, for example, 50

partsof non-splittable sulphonic acid to 100 parts of splittablesulphonic acid. The methods of employment set forth ;in thespecification depend partly on this formation of resistant sulphonicacids. The sulphonated olein with cold test combines certain propertiesfor use in the textile art and this combination distinguishescold-stable oleins from other sulphonated fatty substances. Sulphonatedcold-stable olein is, as was to be expected in view of the lowtemperature atwhich the original solidification commences, poor insaturated fatty acids, i. e.'poor indiflicultly soluble soap formers. Itcontainsno readily oxidizable neutral oils, such as for example,vegetable oils, and no resinifying fatty acids, such as for example,castor oil fatty acids, no deeply coloured polymerized bodies, and nolarge quantities of hydroxy acids, estolides or lactones formed by thesulphonating agent. The product used according to the specification,since it; is made without the use of a solvent, is also not obtained bymeans of chloracetyl chloride sulphonic cold-stable olein containsvariable quantities of non-splittable sulphonic acids, so that it canused both as I 013 the other hand the sulphonated v 1. A brightlycoloured, emulsifying, thin- 1y liquid olein with the typical usualcharac-- terizing values of the non-emulsifying oleins, e. with an'acidvalue of 196,8. sa'ponification 6, va lie of 197, and an iodine'value of8 6, andso forth, as well as [2. A water soluble brightly coloured freestable towards 1 similar known sulphonating agents, preferlably attemperatures above- (1., and for example neutralized the, sulphonicradi-' cal, maybe addedto spinning oils or spin oleins andimthisfllly 'lg gl c trated homogeneous oils are obtamed which are preeminentlyadapted for the spinning and devilling-ofwool owing to their stabili-'ty towards oxygen as shownby the Mackey test'zy l "Minutes Mackeytest0515 so as 120 150 Spinningoilwithoutiron 99 101 101 105 me vfipinningoilwithironn 105 122 Z!) $5 Spinning 011 without iron and withsul- V phonated cold-stabloolein no me 104 120 105Bpin'ningoilwithimnandwithsulpho- V nated wm mmooiunnn; no n1 us 105 1o1 They do not contain any negative catalysts 40 therefore which arealien in kind [non dye- 7 stuff components of the nature ofnaphthols.Whereas an iron-containing olein showed a Mackey test of 200 C. after.95' minutes, therefore, the same iron-containing olein after addition ofsulphonated cold-stable olein I possessed a very favourable-Mackey testof only 105 C. after l20 min'utes. 'If instead of the sulphonatedcold-stable olein the same quantity of turkey red 'oilis addedin the i-known manner to the same iron-containing olein then an unfavourableMackeytest of 200 C. was obtained after only'75 minutes.

i This unfavourable result, which was obtained with a'sulphonatedvegetable oil, is to at which tributed to the strongly unsaturated ofthe said oil.

For example, 500 kg; of an olein is a'clear liquid at +3 C. are cooleddown to a temperature of +3 C. and are gradually combined whilststirringandcooling with 200-500 kg, of a concentrated sulphuric acidwhich had been cooled down to --5C., the

combination being efiected by a known methrature be-' v tween 0 C. andabout +15 C. After the od of'mixing at a-working-tempe usual washingprocess, e; g. with a solution of Glauoer salt, a sulphonation productis obtained havingthe said properties which can be wholly or partiallyneutralized in known manner, or canbe esterified with 'aliphatic orhydro-aromatic alcohols, or "can be mixed with other products, such asfor example, solid soda.

In the same way commercial oleic acid which has been extensively freedfrom solid constituents. by cooling-can be sulphonated under equivalentconditions with chlorsulphonic acid to form aproduct which, besidesoutstandingfrothing' capabilities, in neutral or acid aqueous solutionpossesses high sta-- bility towards lime and boiling and a satis-'factory moistemng,emulsifying and cleans: ing action. r For example, 1prepared as described above, and 3. parts of soap .are mixedtogether toform 9.04% soap solution and may be used for ance' of greasy lime soaps.Again, as an example,

part of sulphonated olein,

100 g. of sulphonat-.

, fulling woolen -wares in soft-or hardwater wit avoid- I ed commercialoleic acid obtained as 'described above are dissolved in 30 litrescf' asulphuric acid'having a concentration of 2: B. and used for acid fullingin the manuface tureof felt in order to produce a satisfac? tory feelandan articlewhich-iawithout smell."

, Asa further example a dye bath is 7 made containing in 1 litre 1-3 g.of oleins sul phonated as described above. The addition.

raisesthe equalizing capmbil v ities during the dyeing operation Whatwerclaim 1. A process'for making sulphonated com- Imercial oleic acidsor oliens consisting in sulphonating commercial oleic acids or oleinswhich have beendestearinized with a sulphonating agent at low A ,procmfor making sulphonated am.

-mercial oleic acids or oleins in sulphonati'ng commercialoleic acids oroleins which have been with sulphuric acid at a low temperature Aprocess for mercial-oleic acids or oleins, consisting in sulphonatingcommercial oleic acids or oleinswith a sulphonating agent-atfa lowtemperature, said oleins having. been previously freed to a. very largeextent of solidfatty acid.

mercial oleic acids or oleins, 'co nsulphonating commercial oleic orioleins 4. A process for making sulphonated com: i

with sulphuric acidat a .lowtanperahlresaid oleins-having beenpreviously td a verylarge extent of solid fatty acid.

.In testimony whereof we have our names to this specification.

Hans KANTOROWICZ.

ARNOLD 'nonnnn;

